JPS59157141A - Synthetic resin composite - Google Patents

Abstract

PURPOSE:A composite consisting of an acrylic rubber-containing styrene resin and a plasticizer-containing vinyl chloride resin, preventing occurrence of cracking on the surface of contact face at the side of the styrene resin, having improved environmental stress cracking resistance. CONSTITUTION:A composite consisting of an acrylic rubber-containing styrene resin obtained by polymerizing an aromatic vinyl monomer or a mixture of it and another monomer copolymerizable with it in the presence of acrylic rubber and a vinyl chloride resin containing >=1wt% plasiticizer. Acrylic rubber having <=10.0(cal/cc)<1/2> solubility parameter and <=10 deg.C, preferably <=0 deg.C glass transition temperature is preferable as the acrylic rubber. Styrene, vinyltoluene, etc. is used as the aromatic styrene and its amount in the monomer mixture is 50- 100wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin composite with improved environmental stress cracking properties comprising a styrene resin containing graft polymerized acrylic rubber and a vinyl chloride resin containing a plasticizer.

Styrenic resin has a wide range of uses due to its excellent mechanical properties and ease of molding, and one of its uses is a ρ composite with vinyl chloride resin containing a plasticizer. .

The composite described here refers to a structure obtained by configuring different resin molded products through contact surfaces, and specifically refers to a double injection molded product, a composite laminate, or an assembled product. There are things etc.

By the way, when a styrene-based resin and a vinyl chloride-based resin/resin containing a plasticizer come into contact, cracks occur in the styrene-based resin on the contact surface, and in severe cases, a phenomenon of breakage frequently occurs. This phenomenon occurs when the plasticizer contained in the vinyl chloride resin migrates to the styrene resin side, and the styrene resin undergoes environmental stress cracking due to the plasticizer. This is due to poor gender.

In an attempt to improve the environmental stress cracking resistance of styrenic resins against plasticizers, it is necessary to increase the molecular weight of the resin, copolymerize a highly polar monomer, increase its content, or include a rubber component. , or increasing its content, but none of these methods resulted in a practically sufficient improvement effect.

For this reason, styrene resin and vinyl chloride resin containing a plastic surface are not normally used in contact with each other.
There were restrictions on the uses of styrene resin.

As a result of extensive research into methods for preventing environmental stress cracking of a composite consisting of a styrene resin and a vinyl chloride resin containing a plasticizer, the present inventor discovered that aromatic vinyl monomers in the presence of acrylic rubber Acrylic rubber-containing styrenic resin obtained by polymerizing a mixture of polymer or aromatic vinyl monomer and other copolymerizable monomers and vinyl chloride containing a plasticizer in a weight ratio of □ or more In the case of synthetic resin composites made of styrene-based resins, it was discovered that cracks do not occur in the styrene-based resin on the contact surface, leading to the completion of the present invention.

The synthetic resin composite produced by Akichi Kinoe eliminates the phenomenon of cracking caused by plasticizer migration, so it is suitable for use in automobile parts, electrical equipment parts, etc.

The acrylic rubber-containing styrenic resin used in the present invention is a graft polymerization method in which an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and other copolymerizable monomers is polymerized in the presence of an acrylic rubber. Obtained by law.

Acrylic co-P1 constituting the acrylic rubber-containing styrenic resin used in the present invention, an acrylic ester phosphor alone or a copolymer, or a copolymer of an acrylic ester monomer and other copolymerizable monomers In Although,
The acrylic acid ester monomers mentioned here include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, glycinol acrylate, etc. Polymerizable monomer t bs ,
Aromatic vinyl monomers such as styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, cyanide vinyl monomers such as acrylonitrile and methacrylate trile, methyl methacrylate, butyl methacrylate,
These include methacrylic acid ester monomers such as glycidyl methacrylate, olefin monomers such as ethylene, propylene, l-butene, inbutylene, and 2-butene, and vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.

In addition, as the acrylic rubber constituting the acrylic rubber-containing styrenic resin used in the present invention, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer in addition to the above monomers can also be used. Examples of the polyfunctional vinyl polymer include divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, l,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl incyanurate. , trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, 1, 3, 5-, , Kosho 49-2459
It is preferable that the polyfunctional vinyl solubility parameter disclosed in Publication No. 7 is 1.0.0 (cal/cc)' or less. However, the Numakaido A used here? The parameter is the solubility parameter value described in "Polymer Handbook" by John = Wiley & 5ons Saito Publishing, and the solubility parameter δT of the copolymer.
is the solubility profile of a single electrolyte of individual vinyl monomers constituting a co-merged consisting of m types of vinyl monomers.
Tar δ. and its weight fraction Wn, it is calculated by equation (1). □For example, polybutyl acrylate,
and the solubility and matrix parameters of polyethyl acrylate are n8-8 (cal/.C) and 9.4 (c
al/. . The bath solubility/e lameter of a copolymer consisting of butyl acrylate 70% by weight and ethyl acrylate/l; 30% by weight is 9. Q ('cal/cc)
' Calculate it. The solubility/layer meter is 1.
Acrylic/L/O” exceeding O-0(ca17oo)k
Using A51, obtained, fl.

A styrenic resin containing acrylic rubber is not preferred because of poor plasticizer resistance.

The acrylic rubber constituting the acrylic rubber-containing styrenic resin used in the present invention (2) has a glass transition temperature of 1
The temperature is preferably 0°C or lower, preferably 0°C or lower.

An acrylic rubber-containing styrenic monomer obtained using an acrylic rubber whose glass transition temperature exceeds 10°C is
Plasticizer resistance is poor and unfavorable.

There are no particular restrictions on the method of polymerizing acrylic rubber, and known techniques such as emulsion polymerization and solution polymerization can be applied.

The acrylic rubber-containing styrenic resin used in the present invention is obtained by polymerizing an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and other copolymerizable monomers in the presence of acrylic rubber. However, the aromatic vinyl monomers mentioned here are styrene, α, ? - methylstyrene,
Other copolymerizable monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate. Yx which(
meth)acrylic acid ester monomers, etc. Examples of preferred monomers or combinations thereof include styrene, styrene-acrylonitrile, styrene-α-methylstyrene-acrylonitrile, styrene-acrylonitrile-methyl methacrylate, styrene-acrylonitrile loop tyl acrylate, etc. .

In the present invention, the monomer to be polymerized in the presence of acrylic rubber preferably contains an aromatic vinyl monomer in an amount of 5.0 to 100% by weight; If the ratio is less than 5ON, the resulting resin will have poor moldability, which is not preferred.

There are no particular restrictions on the method of polymerizing the monomer in the presence of acrylic rubber, and known techniques such as emulsion polymerization, suspension polymerization, bath liquid polymerization, and bulk polymerization can be applied.

The acrylic rubber-containing styrenic resin used in the present invention may be blended with an aromatic vinyl monomer or a polymer consisting of an aromatic vinyl monomer and other copolymerizable monomers, if necessary. Examples of preferred monomers or combinations thereof include styrene, styrene-2-acrylonitrile, styrene-α-methylstyrene-acrylonitrile, α-methylstyrene-acrylonitrile, and styrene-acrylonitrile-methyl methacrylate. There are no particular restrictions on the method for producing the polymer, and known techniques can be applied.

The vinyl chloride resin used in the present invention refers to a homopolymer or a vinyl halide resin having vinyl chloride as a constituent unit.
Olefin monomers such as ljt-form, ethylene, propylene, l-butene, 2-butene, imbutylene, noritrunene, tsene monomers such as butatsuene, isozo, lene, chloroprene, ethyl acrylate, butyl acrylate ,
(Meth)acrynomonomers such as hexyl acrylate, hexyl acrylate, and methyl methacrylate; nitrile monomers such as acrylonitrile and methacrylonitrile;
These include styrene monomers such as styrene, α-methylstyrene, and vinyltoluene, vinyl ether monomers such as methyl vinyl ethyl, ethyl vinyl ether, and phenyl vinyl ether, and fatty acid vinyl monomers such as nyl acetate. can be used alone or in combination.

There are no particular restrictions on the method of polymerizing the vinyl chloride resin, and known σ) techniques such as emulsion polymerization and suspension polymerization can be applied.

Further, the vinyl chloride resin used in the present invention can be mixed with other polymers for modification, and the other polymer used here is ABS.

Poly(methyl methacrylate-butadiene-styrene)
, polymethyl methacrylate, poly(methyl methacrylate-butyl acrylate) L nitrile rubber, epichlorohydrin rubber, EVA, poly(ethylene-zolopyrene) rubber, poly(styrene-butanoene) rubber, and the like.

Further, the vinyl chloride resin used in the present invention contains 1% by weight or more of a plasticizer, and the plasticizers used here include trimethyl phthalate, butyl phthalate, isobutyl phthalate, butyl phthalate, Phthalate esters such as butyl phthalate, butyl phthalate, tunonyl phthalate, diisodecyl phthalate, nodolipyl phthalate, nocyclohexyl phthalate, noisodecyl succinate, nooctyl anopinate, twindecyl anopinate, nooctyl azelaate, butyl sepanate, Aliphatic dibasic acid esters such as sepa/nooctyl tetrahydronate, glycol esters such as diethylene glycol nobenzoate, notaerythritol hexaester, butyl oleate,
Phosphate esters such as methyl acetyl ricinoleate, fatty acid esters, tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, trichloroethyl phosphate, epoxidized fat oil, epoxidized linseed oil, evo Examples include epoxy compounds such as octyl gycisstearate, tricresyl, and tributyl acetyl citrate. These plasticizers alone,
Yes (・ can be used in combination.

The present invention relates to a composite consisting of a styrene resin containing acrylic rubber and a vinyl chloride resin containing a plasticizer of 1 weight factor or more. The figure shows a structure obtained by forming a molded product through a contact surface, such as a double injection molded product, a composite laminate, an assembly, etc.

The double injection molded product refers to a structure in which the contact surfaces of the first injection molded product and the second injection molded product are formed during injection molding of the second injection molded product, and specifically π is the first injection molded product. The second resin is manufactured by injection molding a second resin into a cavity in a mold filled with an injection molded product. To obtain a double injection molded product, a double injection molding machine may be used, or two independent injection molding machines may be used. The double injection molding machine has two injection mechanisms, each of which has two injection mechanisms.

The material is injected separately from the injection mechanism. In some cases, two mold □ clamping mechanisms are provided, but in some cases, two molds have a rotation f6 mechanism in the square mold clamping mechanism. In either case, the molded parts injection-molded from separate injection mechanisms are combined in a mold to form a single molded part.

- When two independent injection molding machines are used, the first injection molding machine injects the first material, and then the molded product is incorporated into the mold of the second injection molding machine, A second injection molding machine injects the second material to obtain a single molded article.

...A composite laminate refers to a structure in which layers each made of different materials are laminated. Composite laminates are generally produced by a lamination method or a coextrusion method, but any of these techniques can be applied to the present invention.

In the lamination method, a composite laminate can be easily obtained by laminating a styrene resin containing acrylic rubber and a vinyl chloride resin sheet with an adhesive. Ordinary styrene-based resins are subject to environmental stress crack failure due to the adhesives used here, but the acrylic rubber-containing styrene-based resin used in the present invention has good resistance to these adhesives. Shows environmental stress cracking.

Co-extrusion methods can be roughly divided into two types: a multi-manifold method and a feed block method. Both of these methods may be applied in the present invention. There are no particular restrictions on the coextrusion technique, and known techniques can be applied as they are. The adhesion between styrene resin and vinyl chloride resin is high, and good coextrusion laminated notebooks can be obtained in the present invention.

The term "assembly" refers to a structure in which separately shaped molded products are assembled with each other through contact surfaces, and can take various forms depending on the application.

The composite of the present invention has an acrylic rubber-containing styrenic resin and a vinyl chloride non-slip resin as essential constituent units, but other resins can be used as constituent units depending on the purpose. Other resins mentioned here include polystyrene, high inno-cyclostyrene, and poly(sunarene-methyl methacrylate).
, ABS, poly(acrylonitrile-EPDM-
Styrenic resins such as styrene (AES), polyethylene, polypropylene, chlorinated resins, styrene, chlorine 1
Noolefin resins such as hyborinolobyrene, polymethyl methacrylate am, -nylon 6, nylon 66, nylon 610. These include polyamide resins such as nylon F112, nylon 11° and nylon 12, polycarbonate resins, polysalvon resins, polyphenylene oxide resins, etc., but styrene resins that cause environmental stress cracking when in contact with vinyl chloride resins, It is preferable to use polymethyl methacrylate resin, polycarbonate resin, etc. while avoiding contact with vinyl chloride resin.

As explained above, the composite of the present invention is a structure whose constituent units are a styrene resin containing acrylic rubber and a vinyl chloride resin, and the styrenic resin containing acrylic rubber has the ability to absorb environmental stress that appears to be a plasticizer. Because it has excellent tearability, cracks do not occur in the acrylic rubber-containing styrene resin at the interface when it comes into contact with the vinyl chloride resin containing a plasticizer. This γ rice, the composite of the present invention, contains polyethylene,
No impact polystyrene, As resin, A'B
Prevents accidents caused by cracks that frequently occur with composites made of styrene resins such as S resins and vinyl chloride resins. Suitable for use in automobile parts, electrical equipment parts, furniture, miscellaneous goods, etc. □ Hereinafter, the present invention will be further explained with reference to Examples.

It is also shown on the stopping standard.

Example 1 Production of acrylic rubber Stainless steel autoclave (150 parts of pure water, 1 part of potassium peracetate, 1 part of dodecyl benzene sulfonic acid)
1.0 part of IJum was added and stirred under a nitrogen atmosphere. Keep the contents at 65°C, add 10 parts of butyl acrylate,
A monomer mixture consisting of 0.23 parts of triallylisocyanurate (2) was added continuously over a period of 5 hours, and the mixture was left to stand for another 5 hours. A monomer mixture consisting of 0.07 parts was continuously added over 1.5 hours, and the polymerization was completed by standing for an additional 2 hours.The average particle size of the latex of the obtained acrylic rubber was Transition temperature: 63℃,
R66 part, grammar meter is 8.8 (1 piece with cal/cc voice.

The composition and properties of the obtained acrylic rubber are summarized in Table 1 as Sample AA.

Acrylic rubbers of Sample A B = G in Table 1 were produced in the same manner, and their compositions and properties are summarized in Table 1.

Production of graft polymer: In a stainless steel autoclave, 250 parts of the acrylic rubber latex (solid content 40%) shown in Table 1, 220 parts of pure water, 0.005 parts of ferrous sulfate, and 0 tetrasodium ethylenediaminetetraacetate were added.
．． 01 MB, sodium formaldehyde sulfoxysilane) was added, and the mixture was stirred under a nitrogen atmosphere.

The contents were maintained at 60 DEG C., and a monomer mixture consisting of 25 parts of acrylonitrile, 75 parts of styrene, 6 parts of t-dodecyl mercaptan, and 15 parts of t-butylhydrooxide was continuously added over 5 hours. Then add the contents to 7
The polymerization was completed by stirring at 0.00 °C for 2 hours.

An aqueous solution containing 8 parts of calcium chloride was added to the obtained latex and stirred at 95C for 3 minutes to obtain a precipitate.

This precipitate was dehydrated, washed with water, and dried to obtain a resin powder.

40 parts of the resin powder was mixed with acrylonitrile) I + loose styrene copolymer AS) fH resin-acrylonitrile content 2
7%) 60 parts, 2,6-not-t-butyl-4-methylphenol o', 0.0 parts triphenylphosphite. t
81s and 2.0 parts of ethylene bis stearylamide were mixed together and fed to an extruder to obtain an acrylic rubber-containing styrenic resin (AAS resin) pellet.

This AAS resin was used as rs80CN-V manufactured by Toshiba Machine Co., Ltd.
Injection molded with an injection molding machine at a molding temperature of 220C,
One plate-shaped molded product of 0 x 30 x 3 mm was obtained.

This molded product was fitted into a mold with cavity dimensions of 200 x 30 x 6 mm, and one sample J16.
H--N vinyl chloride solution was injection molded at a molding temperature of 150C to obtain a double injection molded product.

The environmental stress cracking resistance of the obtained square injection molded product was evaluated by the following method.

1) Q) A double injection molded product is strained for 30 minutes, fixed in a jig, and left in a constant temperature bath at 60C for 5 days.

11) After 5 days, the molded product was removed from the jig, the vinyl chloride layer was peeled off, and the surface condition of the AAS resin molded product was observed.

11i) AAS resin Resin molding physical boundary stress cracking resistance was evaluated by the following method, and the results are summarized in Table 3.

l: Almost no change ■; Fine cracks occur at both ends of the molded product ■; Fine cracks cross the molded product.

■; Thick crack crosses the molded product V; Crack grows on the floor (grows and breaks immediately when bent) ■; Composite laminate that breaks A 7'4? round was coextruded using a multi-manifold die.

Here, the extrusion temperature of AAS resin is 200C.

The extrusion temperature of the vinyl chloride compound was 1700°C, and the multi-manifold die temperature was 180°C. Also,
The AAS resin σ) sheet thickness was 2wn, and the vinyl chloride concrete sheet thickness was 1.

This joint push, push out sea. A strip of 200 x 30 x 3 cylinders was cut out from the sheet, and environmental stress and crack resistance were evaluated according to the following method.

1) Fix the test piece to a jig with 5 (L) distortion,
Leave it in a thermostat at 50C for 5 days.

11) After 5 days, the molded product was removed from the jig, the vinyl chloride layer was peeled off, and the surface condition of the AAS ml resin sheet was observed.

1ii) The environmental stress cracking resistance of the AAS lj resin sheet was evaluated by the following method.

■= Almost no change ■: Both ends of the test piece! L: A fine crack occurs lI: A fine crack crosses the test piece ■: A thick crack crosses the test piece V: The crack grows deep and breaks immediately when bent ■; Evaluation of rupture The results are shown in Table 4.

Assemble this AAS resin to IS80CN-V manufactured by Toshiba Machine Co., Ltd.
Injection molding was performed using an injection molding machine at a molding temperature of 220 C to obtain a cylindrical molded product with an inner diameter of 30 mm, an outer diameter of 34 mm, and a height of 70 mm.

Separately, samples AH, I, and J shown in Table 2 were vinyl chloride.
Molding the gland with the above injection molding machine / 1 type degree 1600
Injection molded, inner diameter 25mm, outer diameter? '! :30mm,
A cylindrical molded product with a height of 80+mm was obtained.The vinyl chloride compound molded product and the AAS resin molded product were pressed together to form an assembly.

I-) The environmental stress cracking resistance of the slat assembly was evaluated using the method described above.

1) Leave this assembly for 7 days at 8 o'clock in the temple.

11) After 7 days, remove the gunpowder and use A A S @j
Observe the surface roughness of the fat molded product.

111) The environmental stress cracking resistance of the AAS resin molded product is evaluated by the following method.

l; remains almost unchanged 11; A few small cracks occur 11; Many small cracks occur 1v: A thick crack occurs V: The crack is deep (grows and breaks immediately after bending) ■; to fall into ruin The evaluation results are shown in Table 5.

Example 2 62.5 parts of acrylic rubber latex (solid content 40%) of Sample 1A in Table 1 and 1 part of pure water were placed in a Sudenless autoclave.
95 parts, 0.0045 t of ferrous acetate! A5. Add 0.01 part of tetrastorium ethylenenoaminetetraacetate and 0.3 part of sodium formaldehyde sulfoxylate, and stir under nitrogen atmosphere. The contents were maintained at 60 fC, and 40 parts of styrene, 20 parts of α-methylstyrene, 15 parts of methyl methacrylate, 25 parts of acrylonitrile, t-dodecyl, 0.45 parts of mercaptan, and t-butyl hydro/
A monomer mixture consisting of 0.1'5 parts of
It was added continuously over time. The contents were then stirred at 70°C for 4 hours to complete the polymerization.A water bath solution containing 5 parts of calcium chloride was added to the obtained latex and stirred at 95G for 3 minutes to form a precipitate. This precipitate was dehydrated, washed with water, and dried to obtain a resin powder.

To 100 parts of this resin powder, 2.6-not-t-butyl-4
- 0.1 part of methylphenol, 0.1 part of triphenyl phosphite, and 2.0 parts of ethylene bisstearylamide were added and fed into an extruder to form an AAS 1'llll-sized pellet.

Example 1'Li method vc, ft,', obtained r'L,
A two-car injection molded product was prepared from one AAS resin beret and vinyl chloride compound Q-land of Sample A I (Table 2), and the environmental stress cracking property was evaluated and the degree of cracking was I.

Example 3 In place of the monomer mixture of Example 2, 1'OO parts of styrene,
Acrylic rubber-containing styrenic resin -ξ The obtained acrylic rubber-containing styrenic styrenic resin crosslinked red and Table 2 sample JE were then subjected to the method described in Example 1.
A double injection molded product was prepared from H vinyl chloride and a land, and the environmental stress cracking resistance was evaluated.

Example 4 Example 1'/c Method 'Lf: Pitax V
-6100AHT1V-61UOAP.

and V-6101A'H (both AAS resins manufactured by Hitachi Chemical Co., Ltd.) and PVC of Table 2 Samples A and H.
Double-injection molded products were made from Gland and Karaso T, and their environmental stress cracking properties were evaluated.
Met.

Comparative Example 1 In Examples 1.2 and 3, except that polybutanoene (average particle size 0.4 μm) latex was used instead of acrylic rubber, a graph-titt composite was produced in the same manner as in the example, and a resin pellet was formed. Obtained.

Next, according to the method shown in Example 1, double injection molded products were made from the obtained resin coating and 9 rounds of vinyl chloride compound of sample AH in Table 2, and the environmental stress cracking properties were evaluated. The level of n was also very poor.

Comparative Example 2 Polystyrene resin (MW-1 manufactured by Nemiki Kagaku Kogyo Co., Ltd.)
, and AS resin (As-H manufactured by Denki Kagaku Kogyo Co., Ltd.) and vinyl chloride condensate/de and Karaso of Table 2 Sample &H
A double extrusion molded product was prepared for each, and the environmental stress cracking properties were evaluated.The degree of cracking was evaluated as ■, which was very poor.

Claims (1)

[Claims] an acrylic rubber-containing styrenic resin obtained by polymerizing an aromatic vinyl monomer or a mixture of a G-cho aromatic vinyl monomer and other copolymerizable monomers in the presence of acrylic rubber; A synthetic resin composite made of vinyl chloride resin containing a plasticizer in excess of its weight coefficient.